CN108463285A

CN108463285A - Fluidized catalytic cracking catalyst for improving butylene yield

Info

Publication number: CN108463285A
Application number: CN201680078540.9A
Authority: CN
Inventors: K·C·卡拉斯
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2015-11-24
Filing date: 2016-11-18
Publication date: 2018-08-28
Anticipated expiration: 2036-11-18
Also published as: EP3380231A1; RU2736077C2; BR112018010444B1; JP2018536535A; EP3380231A4; US10507460B2; BR112018010444A8; RU2018122244A3; US20200101448A1; US11027264B2; US20180369793A1; KR20180075687A; JP6873133B2; BR112018010444A2; WO2017091472A1; CN108463285B; CA3006197A1; RU2018122244A

Abstract

Microballoon fluidized catalytic cracking catalyst includes zeolite and alkali metal alkaline earth metal ion.

Description

Fluidized catalytic cracking catalyst for improving butylene yield

Cross reference to related applications

It is described this application claims the priority for the U.S. Provisional Application No. 62/259,368 submitted on November 24th, 2015 The full content of application is incorporated herein by reference.

Technical field

The technology of the present invention relates generally to petroleum refining catalyst.More specifically, this technology is related to including zeolite and alkali Microballoon fluid catalytic cracking (the microspherical fluid catalytic of metal ion or alkaline-earth metal ions cracking；FCC) catalyst, and the method for preparing and use this kind of catalyst.

Invention content

In an aspect, the microballoon fluidized catalytic cracking catalyst disclosed herein for including Y- zeolites and barium ions.

In another aspect, the microspherical catalyst disclosed herein for including about 3.3wt.% barium ions, wherein catalyst have There is the phase including about 18wt.%Y- zeolites, about 30wt.% mullites, about 2wt.% anatases and about 50wt.% amorphous materials Composition.

In another aspect, the method disclosed herein for preparing microballoon fluidized catalytic cracking catalyst, includes the following steps： (a) microsphere is made to be mixed with barium solution；(b) microsphere of calcining step (a)；Wherein microsphere is included in porous salic Crystallization is the Y- zeolites of layer on the surface of matrix.

Description of the drawings

Fig. 1 illustrates to become with containing the barium content in titanate catalyst, or in illustration with containing the lanthanum content in lanthanum catalyst and The unit cell dimension of the Y- zeolites steamed become.

Fig. 2 illustrates to become with containing the barium content in titanate catalyst, or in illustration with containing the lanthanum content in lanthanum catalyst and The surface area for steaming Y- zeolites become.

Fig. 3 illustrates with the substrate surface area steamed become containing the barium content in titanate catalyst.

Fig. 4 illustrates the estimated activity under catalyst/oil=5 become with dopant content.

Fig. 5 illustrates the gasoline for the catalyst for containing 0.7-1.1wt.% barium compared to 1.4wt.% lanthana comparative catalysts Selectivity.

Fig. 6 illustrates to contain urging for 2.0-3.3wt.% barium compared to 1.2wt.% or 3.5wt.% lanthana comparative catalysts The gasoline selective of agent.

Fig. 7 illustrates the coke selectivity containing titanate catalyst compared with containing lanthanum catalyst.

Fig. 8 illustrates in baric or liquefied petroleum gas (liquefied petroleum under the given conversion ratio containing lanthanum catalyst gas；LPG productivity).

Fig. 9 illustrates the isobutene become with baric or containing the conversion ratio of lanthanum catalyst/iso-butane ratio.

Specific implementation mode

Various embodiments are described below.It should be noted that specific embodiment is not intended as exhaustive description or to herein The limitation of discussed more broadly aspect.The one side need not be confined to that embodiment in conjunction with specific embodiments, and Any other embodiment can be utilized to implement.

As used herein, it will be " about " those skilled in the art's understanding and will depend on to a certain extent The case where its use and change.If the term that do not known using those skilled in the art, in view of its use The case where, " about ", which will imply that, reaches positive the 10% or minus 10% of specific term.

Unless herein in addition instruction or clearly contradicted with content, otherwise in the case where describing element (especially with In the case of lower claims) using term " one (a/an) " and " described " and it is similar refer to object should be interpreted that cover it is singular And plural number.Unless in addition instruction herein, is otherwise intended merely to serve as individual refer to the narration of this paper median value ranges and belongs to institute The stenography method of each single value of range is stated, and each single value is incorporated in this specification, as herein individually Narration is general.Unless otherwise indicated herein or in addition it is contradicted with content, otherwise all methods as described herein can be by any Suitable sequence carries out.Unless otherwise stated, any and all examples or exemplary language provided herein (such as " such as ") use be intended merely to that embodiment is better described, and the scope of claims is not limited.In specification Language should be construed as indicating that the element of any failed call is essential.

Fluid catalytic cracking

Catalytic cracking, and especially fluid catalytic cracking (FCC) is usually used in converting heavy hydrocarbon feeds to lighter product, such as Gasoline and distillate range fraction.However, needing day to the light olefins yields in the product form of raising catalytic cracking process Benefit improves.Light olefin (C2-C4 alkene) is the important source material of petrochemical industry.For example, each molecule has four carbon atom Light olefin butylene be for producing other useful materials, such as the important chemical of gasoline alkylate.

To produce light olefin, the catalytic cracking of heavy hydrocarbon feeds (such as naphtha) usually by make containing naphtha feed with usually The carbon monoxide-olefin polymeric contact being made of one or more crystalline micro porous molecular sieves is selectively converted to contain alkene to feed Hydrocarbon mixture carries out.Although in the past having proposed various naphtha catalytic cracking process, but much techniques do not produce and have The commercially important light olefin of enough selectivity or yield, such as butylene.In contrast, practical and economic naphtha catalysis Process should selectively produce the light olefin of incrementss, such as butylene, while generate minimal amount of methane, aromatic series and coke Charcoal.

In FCC techniques, hydrocarbon raw material is injected to the riser section of FCC reactors, wherein raw material is being contacted from catalyst regeneration Device is cracked into lighter, more value product when being recycled to the thermocatalyst of riser reactors.With in morning the 1960s There is important breakthrough in the introducing of phase molecular sieve or zeolite, FCC catalyst.These materials are incorporated into the FCC catalyst constituted at that time Amorphous and/or amorphous/kaolin material matrix in.These new zeolite catalysts are in silica, aluminium oxide, two It is boiled containing crystalline aluminosilicate in amorphous or amorphous/kaolin matrix of silica-alumina, kaolin, clay etc. Stone, be used for the expression activitiy morning of crackene contains amorphous or amorphous/kaolinic silica-alumina catalyst It is at least 1,000-10,000 times high.The introducing of zeolitic cracking catalyst thoroughly changes fluid catalytic cracking process.Research and develop new work Skill handles these high activities, such as riser cracking, time of contact of shortening, new regeneration technology, new improved zeolite catalysis Agent progress etc..

Zeolite commonly used in FCC is the crystalline aluminosilicate for having uniform crystal structure, the spy of the crystal structure Sign is the regular small holes interconnected by a large amount of or even smaller channel.It was found that by means of single-size hole by interconnecting and logical This structure of the network composition in road, crystalline zeolite can receive size less than a certain molecule for clearly defining value for suction It receives, while repelling the molecule of large-size, and it has been referred to as " molecular sieve " for this reason.This feature structure is also It provides catalysis characteristics, is converted particularly for certain form of hydrocarbon.

In current business practice, most of FCC Cracking catalyst that the whole world uses are by catalytic active component macropore Zeolite is made.Conventional large pore molecular sieve includes X zeolite；REX；Zeolite Y (or Y- zeolites)；Overstable Y (USY)；Rare earth exchanged Y (REY)；The USY (REUSY) of rare earth exchanged；Dealuminzation Y (DeAIY)；Super-hydrophobicity Y (UHPY)；And/or dealuminzation is rich in silicon Zeolite, such as LZ-210.Also ZSM-20, zeolite L and naturally occurring zeolite, such as faujasite, modenite have been used.

Current techniques

Having now surprisingly discovered that alkali or alkaline earth metal exchanges replaces lanthanum to exchange to zeolite the butylene choosing obtained with raising Higher butene fraction in selecting property, lower coke production rate, lower hydride metastasis tendency and liquefied petroleum gas (LPG) Catalyst.

Therefore, in an aspect, the microballoon disclosed herein for including zeolite and alkali metal ion or alkaline-earth metal ions FCC catalyst.It is disclosed herein that the method and its application method for preparing this kind of FCC catalyst is also disclosed.In some embodiments, Alkali metal ion or alkaline-earth metal ions are selected from cesium ion and barium ions.In some embodiments, zeolite includes Y- zeolites.One In a little embodiments, microballoon FCC catalyst includes Y- zeolites and barium ions.

Zeolite includes but not limited to that Y- zeolites, overstable Y, dealuminzation Y (DeAIY), super-hydrophobicity Y (UHPY), dealuminzation are rich in The zeolite (such as LZ-210) of silicon, ZSM-20, zeolite L, naturally occurring zeolite (such as faujasite, modenite etc.), with And other zeolites and any combination thereof known to those skilled in the art.

FCC catalyst has the phase composition that may include at least 5wt.% zeolites.In some embodiments, FCC catalyst has There is the phase composition for including at least 10wt.% zeolites.In some embodiments, FCC catalyst has including at least 15wt.% zeolites Phase composition.In some embodiments, FCC catalyst has the phase composition for including at least 16wt.% zeolites.In some embodiments In, FCC catalyst has the phase composition for including at least 17wt.% zeolites.In some embodiments, FCC catalyst, which has, includes At least phase composition of 18wt.% zeolites.In some embodiments, FCC catalyst has the phase group for including at least 19wt.% zeolites At.In some embodiments, FCC catalyst has the phase composition for including at least 20wt.% zeolites.In some embodiments, FCC Catalyst has the phase composition for including at least 25wt.% zeolites.In some embodiments, it includes at least that FCC catalyst, which has, The phase composition of 30wt.% zeolites.In some embodiments, FCC catalyst has the phase composition for including at least 35wt.% zeolites. In some embodiments, FCC catalyst has the phase composition for including at least 40wt.% zeolites.In some embodiments, FCC is urged Agent has the phase composition for including at least 45wt.% zeolites.In some embodiments, it includes at least that FCC catalyst, which has, The phase composition of 50wt.% zeolites.In some embodiments, FCC catalyst has the phase composition for including at least 55wt.% zeolites. In some embodiments, FCC catalyst has the phase composition for including at least 60wt.% zeolites.In some embodiments, FCC is urged Agent has the phase composition for including at least 65wt.% zeolites.In some embodiments, it includes at least that FCC catalyst, which has, The phase composition of 70wt.% zeolites.In some embodiments, FCC catalyst have including about 5,6,7,8,9,10,11,12,13, 14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、 39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、54、55、56、57、58、59、60、61、62、63、 64, the phase composition of 65,66,67,68,69 or 70wt.% (including wherein increment) zeolite.In some embodiments, FCC catalyst With the phase composition including about 5wt.% to about 25wt.% zeolites.In some embodiments, it includes about that FCC catalyst, which has, Phase compositions of the 10wt.% to about 20wt.% zeolites.In some embodiments, FCC catalyst has including about 10wt.% to about The phase composition of 35wt.% zeolites.In some embodiments, FCC catalyst has including about 10wt.% to about 50wt.% zeolites Phase composition.

FCC catalyst has the phase composition that may include at least 5wt.%Y- zeolites.In some embodiments, FCC catalyst With the phase composition for including at least 10wt.%Y- zeolites.In some embodiments, it includes at least 15wt.% that FCC catalyst, which has, The phase composition of Y- zeolites.In some embodiments, FCC catalyst has the phase composition for including at least 16wt.%Y- zeolites.One In a little embodiments, FCC catalyst has the phase composition for including at least 17wt.%Y- zeolites.In some embodiments, FCC is catalyzed Agent has the phase composition for including at least 18wt.%Y- zeolites.In some embodiments, it includes at least that FCC catalyst, which has, The phase composition of 19wt.%Y- zeolites.In some embodiments, FCC catalyst has the phase group for including at least 20wt.%Y- zeolites At.In some embodiments, FCC catalyst has the phase composition for including at least 25wt.%Y- zeolites.In some embodiments, FCC catalyst has the phase composition for including at least 30wt.%Y- zeolites.In some embodiments, it includes extremely that FCC catalyst, which has, The phase composition of few 35wt.%Y- zeolites.In some embodiments, FCC catalyst has the phase for including at least 40wt.%Y- zeolites Composition.In some embodiments, FCC catalyst has the phase composition for including at least 45wt.%Y- zeolites.In some embodiments In, FCC catalyst has the phase composition for including at least 50wt.%Y- zeolites.In some embodiments, FCC catalyst has packet Include the phase composition of at least 55wt.%Y- zeolites.In some embodiments, FCC catalyst has including at least 60wt.%Y- zeolites Phase composition.In some embodiments, FCC catalyst has the phase composition for including at least 65wt.%Y- zeolites.In some implementations In example, FCC catalyst has the phase composition for including at least 70wt.%Y- zeolites.In some embodiments, FCC catalyst has Including about 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, 30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、54、 55, the phase of 56,57,58,59,60,61,62,63,64,65,66,67,68,69 or 70wt.% (including wherein increment) Y- zeolites Composition.In some embodiments, FCC catalyst has the phase composition for including about 5wt.% to about 25wt.%Y- zeolites.At some In embodiment, FCC catalyst has the phase composition for including about 10wt.% to about 20wt.%Y- zeolites.In some embodiments, FCC catalyst has the phase composition for including about 10wt.% to about 35wt.%Y- zeolites.In some embodiments, FCC catalyst With the phase composition including about 10wt.% to about 50wt.%Y- zeolites.

FCC catalyst has the phase composition that can also include amorphous material.Illustrative amorphous material includes but unlimited In silica-alumina.In other embodiments, amorphous material can derive from the disintegration of crystalline zeolite.Again another In outer embodiment, amorphous material can derive from the disintegration of crystalline Y- zeolites.

FCC catalyst can have the phase composition for further comprising at least about 30wt.% amorphous materials.In some embodiments In, phase composition further comprises at least about 35wt.% amorphous materials.In some embodiments, phase composition further comprise to Few about 40wt.% amorphous materials.In some embodiments, phase composition further comprises at least about 45wt.% amorphous materials. In some embodiments, phase composition further comprises at least about 50wt.% amorphous materials.In some embodiments, phase composition Further comprise at least about 55wt.% amorphous materials.In some embodiments, phase composition further comprise about 25,26,27, 28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、 53、54、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、 78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94 or 95wt.% (including wherein increment) amorphous Shape material.In some embodiments, phase composition further comprises about 25wt.% to about 55wt.% amorphous materials.In some realities It applies in example, phase composition further comprises about 25wt.% to about 50wt.% amorphous materials.In some embodiments, phase composition into One step includes about 30wt.% to about 50wt.% amorphous materials.In some embodiments, phase composition further comprises about 35wt.% is to about 50wt.% amorphous materials.In some embodiments, phase composition further comprises about 35wt.% to about 75wt.% amorphous materials.In some embodiments, phase composition further comprises about 35wt.% to the amorphous materials of about 95wt.% Material.

FCC catalyst has the phase composition that can further comprise mullite.In some embodiments, phase composition is further wrapped Include at least about 20wt.% mullites.In some embodiments, phase composition further comprises at least about 25wt.% mullites.One In a little embodiments, phase composition further comprises at least about 30wt.% mullites.In some embodiments, phase composition is further wrapped Include at least about 35wt.% mullites.In some embodiments, phase composition further comprise about 20,21,22,23,24,25,26, 27,28,29,30,31,32,33,34,35wt.% (including wherein increment) mullite.In some embodiments, phase composition is into one Step includes about 20wt.% to about 35wt.% mullites.In some embodiments, phase composition further comprises about 20wt.% to about 30wt.% mullites.In some embodiments, phase composition further comprises about 25wt.% to about 35wt.% mullites.

FCC catalyst has the phase composition that can further comprise anatase.In some embodiments, phase composition is further wrapped Include at least about 0.5wt.% anatases.In some embodiments, phase composition further comprises at least about 1.0wt.% anatases. In some embodiments, phase composition further comprises at least about 1.5wt.% anatases.In some embodiments, phase composition is further Including at least about 2.0wt.% anatases.In some embodiments, phase composition further comprises at least about 2.5wt.% anatases. In some embodiments, phase composition further comprises at least about 3.0wt.% anatases.In some embodiments, phase composition is into one Step including about 0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1, 2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3.0、3.5、4.0、4.5、5.0、5.5、6.0、6.5、7.0、7.5、8.0、 8.5,9.0,9.5 or 10wt.% (including wherein increment) anatase.In some embodiments, phase composition further comprises about 0.5wt.% is to about 5.0wt.% anatases.In some embodiments, phase composition further comprises about 0.5wt.% to about 4.0wt.% anatases.In some embodiments, phase composition further comprises about 0.5wt.% to about 3.0wt.% anatases. In some embodiments, phase composition further comprises about 1.0wt.% to about 5.0wt.% anatases.In some embodiments, phase group At further comprising about 1.0wt.% to about 4.0wt.% anatases.In some embodiments, phase composition further comprises about 1.0wt.% is to about 3.0wt.% anatases.In some embodiments, phase composition further comprises about 1.0wt.% to about 2.0wt.% anatases.

FCC catalyst can be with the phase composition for including zeolite, mullite and amorphous material.In some embodiments, FCC Catalyst is with the phase composition for including zeolite, mullite, anatase and amorphous material.

FCC catalyst can be with the phase composition for including Y- zeolites, mullite and amorphous material.In some embodiments, FCC catalyst is with the phase composition for including Y- zeolites, mullite, anatase and amorphous material.

FCC catalyst average particle size can be about 60 to about 100 microns.In some embodiments, FCC catalyst is averaged Granularity is about 60 to about 90 microns.In some embodiments, the average particle size of FCC catalyst is about 60 to about 80 microns.One In a little embodiments, the average particle size of FCC catalyst is about 60 to about 70 microns.In some embodiments, FCC catalyst is averaged Granularity is about 80 to about 100 microns.In some embodiments, the average particle size of FCC catalyst is about 70 to about 90 microns.One In a little embodiments, the average particle size of FCC catalyst is about 70 to about 100 microns.In some embodiments, FCC catalyst is flat Equal granularity is about 60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81, 82,83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99 or 100 microns.

In some embodiments, zeolite is incorporated into amorphous adhesive.In some embodiments, zeolite is Y- boilings Stone.Suitable adhesive include but not limited to silica, silica-alumina, aluminium oxide, clay (such as kaolin) or Other known inorganic bond.In some embodiments, transitional alumina, such as γ-Al₂O₃、η-Al₂O₃、δ-Al₂O₃、θ- Al₂O₃、κ-Al₂O₃Or any combination thereof be included in composition.In some embodiments, it prepares and contains zeolite and one kind or more The slurries of kind adhesive are simultaneously spray-dried to obtain the microsphere that average particle size is about 60 to about 100 microns.In some realities It applies in example, slurries further contain aluminium oxide.In some embodiments, slurries further contain clay.In some embodiments, Slurries further contain aluminium oxide and clay.Any effective adhesive can be used；Particularly efficient adhesive includes but not It is limited to chloride hydrate Aluminum sol, silicon dioxide gel and aluminum phosphate.

Y- zeolites can be generated by the program in situ described in U.S. Patent No. 4,493,902 (" ' 902 patent ") Full content for high zeolite content microsphere, the teachings of the patent is herein incorporated by reference.' 902 patents are public Open the FCC catalyst including wear-resisting, high zeolite content, catalytic activity microsphere, the microsphere contains more than about 40%, preferably 50-70 weight %Y faujasites, and it is this kind of to prepare more than about 40% sodium Y- crystallization of zeolites in porous microsphere body by making The method of catalyst, the porous microsphere body (are undergone and the relevant strong endothermic of dehydroxylation by metakaolin through calcining Reaction) and than for by kaolin be converted into those of metakaolin condition more acutely under conditions of the kaolin calcined, i.e., Through calcining with the mixing of the kaolin of experience marks kaolin exothermic reaction (the sometimes referred to as spinel form of calcined kaolin) Object is constituted.The microsphere of two kinds of forms containing calcined kaolin can be also immersed in the alkaline sodium silicate solution of heating, preferably Ground in microsphere until crystallizing obtainable the maximum amount of Y faujasites.

When implementing the invention described in ' 902 patents, make by undergoing exothermic kaolin and metakaolin through calcining The microsphere of composition is reacted with the sodium silicate solution rich in caustic alkali in the presence of crystallization inducer (crystal seed) thus by microsphere In silica and aluminium oxide be converted into synthesis sodium faujasite (Y- zeolites).Microsphere is set to be detached with sodium silicate mother liquor, with Rare earth, ammonium ion or both ion exchange are to form the various known stable forms of rare earth or catalyst.The technology of ' 902 patents There is provided for realizing with high activity, good selectivity and thermal stability and wear-resisting relevant high zeolite content expectation and uniqueness Combination means.

In some embodiments, ' 902 the synthesis sodium faujasite of patent carries out barium ions exchange to form the present invention's The Y- zeolites of FCC catalyst.

Y- zeolites can be produced as microsphere of zeolite body, referred to as come from BASF (BASF)Catalysis Agent is disclosed in U.S. Patent No. 6,656,347 (" ' 347 patent ") and the 6th, 942, No. 784 (" ' 784 patent "), described Two patents are incorporated herein by reference in its entirety.These microsphere of zeolite bodies are macropores, great with enough contents Activity simultaneously has the zeolite of the unique form to realize that effective conversion of the hydrocarbon to cracked-gasoline products, the gasoline products have short The improved bottoms of the lower cracking of time of contact FCC processing.These microsphere of zeolite bodies are generated by novelty processing, described new Grain husk processing is the modification of the technology described in ' 902 patents.If having found the nonzeolite of catalyst, rich salic base Matter is derived from so that 90wt.% hydrous kaolin particles are less than 2 microns of particle size and through crushing and passing through heat release The ultra-fine hydrous kaolin source of calcining, then generating large pore zeolite microsphere.In more general terms, being adapted to carry out FCC catalysis The macroporous FCC catalyst matrix of agent derives from the alumina source with specified water pore volume, as calcined by heat release Kaolin is different from the kaolin for the prior art calcining for being used to form catalyst substrates.Water pore volume derives from patent It is described initial point is slurried (to be initially slurried a little；ISP it) tests.

The form for being formed by the microspheroidal catalyst of ' 347 patents and ' 784 patents is micro- relative to the original position being previously formed Sphere catalyst is unique.Using what is calcined by heat release the original with macroporous structure is obtained through crushing ultra-fine hydrous kaolin Position microsphere of zeolite body, wherein the macropore of structure is substantially coated with or is lined with zeolite after crystallization.It is big as herein defined Hole means that catalyst has and presses 600-20,000 angstroms of mercury at least 0.07cc/gm pressures mercury, preferably at least 0.10cc/gm Macrovoid volume in the range of hole.This catalyst is optimal for FCC processing, and the FCC processing includes wherein making hydrocarbon Class charging contacts the short contacting time processing of about 3 seconds or less time with catalyst.

In the broadest sense, as described in ' 347 patents and ' 784 patentsIt is not limited to have It is derived only from the macroporous catalyst of kaolinic nonzeolite matrix.Therefore, it is possible to use having porosity during zeolite synthesizes With it is reactive appropriately combined and required catalyst macrovoid and any alumina source of form can be generated.Required shape State includes matrix fully dispersed in catalyst, and the big hole wall of matrix is lined with zeolite and is applied substantially free of adhesive Material.Therefore, not only the big aperture surface area of catalyst is greatly improved relative to previous catalyst, but also disperses the work throughout microsphere Property matrix, zeolite crystal can have easy access to hydrocarbon feed.It is not intended to be fettered by any theory of operation, it appears that wherein zeolite passes through Physical mixed is incorporated into matrix and has enough macrovoids with the previous catalyst of adhesive bonding；However, adhesive is coated with Active zeolite catalyst and then obstruction arrive accessibility thereon.Microspheroidal catalyst has following Form：Its since the macrovoid of matrix and the dispersibility of raising allow to be diffused rapidly in catalyst, and due to zeolite freedom It is applied to the highest accessibility that zeolite is further provided on pore wall.Term " freely " means that zeolite is mutually present in base It is hindered on the surface of matter and not by any adhesive phase.Only there is macrovoid not provide acquired as a result, because conventional The catalyst being incorporated to has similar macrovoid.Therefore the combination of porosity and the big hole wall of zeolite coating provides unexpected choosing Selecting property result.

In some embodiments, FCC catalyst includes the zeolite that alkali metal ion exchanges.In some embodiments, FCC is urged Agent includes the zeolite that caesium exchanges.In some embodiments, FCC catalyst is included in in-situ crystallization in porous kaolin matrix The zeolite that caesium exchanges.In some embodiments, it is layer that zeolite crystallizes on the surface of porous alumina-containing matrix.In other implementations In example, matrix derives from the kaolin calcined by heat release.

In some embodiments, FCC catalyst includes the Y- zeolites that alkali metal ion exchanges.In some embodiments, FCC Catalyst includes the Y- zeolites that caesium exchanges.In some embodiments, FCC catalyst is included in in-situ junction in porous kaolin matrix The Y- zeolites that brilliant caesium exchanges.In some embodiments, it is layer that Y- zeolites crystallize on the surface of porous alumina-containing matrix. In other embodiments, matrix derives from the kaolin calcined by heat release.

In some embodiments, FCC catalyst includes at least about 0.3wt.% cesium ions.In some embodiments, FCC is urged Agent includes at least about 0.4wt.% cesium ions.In some embodiments, FCC catalyst include at least about 0.5wt.% caesiums from Son.In some embodiments, FCC catalyst includes at least about 0.6wt.% cesium ions.In some embodiments, FCC catalyst Including at least about 0.7wt.% cesium ions.In some embodiments, FCC catalyst includes at least about 0.8wt.% cesium ions. In some embodiments, FCC catalyst includes at least about 0.9wt.% cesium ions.In some embodiments, FCC catalyst includes extremely Few about 1wt.% cesium ions.In some embodiments, FCC catalyst includes at least about 2wt.% cesium ions.In some embodiments In, FCC catalyst includes at least about 3wt.% cesium ions.In some embodiments, FCC catalyst includes at least about 4wt.% caesiums Ion.In some embodiments, FCC catalyst includes at least about 5wt.% cesium ions.In some embodiments, FCC catalyst Including about 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,2,3,4,5,6,7,8,9 or 10wt.% (including wherein increment) caesium Ion.In some embodiments, FCC catalyst includes about 0.3wt.% to about 5wt.% cesium ions.In some embodiments, FCC catalyst includes about 2wt.% to about 5wt.% cesium ions.In some embodiments, FCC catalyst is arrived including about 2wt.% About 4wt.% cesium ions.

In some embodiments, FCC catalyst includes the Y- zeolites that alkaline-earth metal ions exchange.In some embodiments, FCC catalyst includes the Y- zeolites that barium exchanges.In some embodiments, FCC catalyst is included in porous kaolin matrix Central Plains The Y- zeolites that the barium of position crystallization exchanges.In some embodiments, Y- zeolites crystallize on the surface of porous alumina-containing matrix is Layer.In other embodiments, matrix derives from the kaolin calcined by heat release.

Y- zeolite unit cells can include barium ions at ion exchange site III.The tuple of position III is 96.In some realities It applies in example, Y- zeolite unit cells include about 0.5 to 10 barium atoms at ion exchange site III.In some embodiments, Y- boils Stone structure cell includes about 4 barium atoms at ion exchange site III.In some embodiments, barium ions does not occupy Y- zeolites The ion exchange site I ' and II ' of structure cell.In some embodiments, Y- zeolite unit cells include barium at ion exchange site III Ion and barium ions does not occupy ion exchange site I ' and II '.

In some embodiments, by x-ray diffraction, the no more than about barium ions of half can be located on zeolite.One In a little embodiments, by x-ray diffraction, the no more than about barium ions of half can be located on Y- zeolites.

In some embodiments, FCC catalyst includes at least about 0.3wt.% barium ions.In some embodiments, FCC is urged Agent includes at least about 0.4wt.% barium ions.In some embodiments, FCC catalyst include at least about 0.5wt.% barium from Son.In some embodiments, FCC catalyst includes at least about 0.6wt.% barium ions.In some embodiments, FCC catalyst Including at least about 0.7wt.% barium ions.In some embodiments, FCC catalyst includes at least about 0.8wt.% barium ions. In some embodiments, FCC catalyst includes at least about 0.9wt.% barium ions.In some embodiments, FCC catalyst includes extremely Few about 1wt.% barium ions.In some embodiments, FCC catalyst includes at least about 2wt.% barium ions.In some embodiments In, FCC catalyst includes at least about 3wt.% barium ions.In some embodiments, FCC catalyst includes at least about 4wt.% barium Ion.In some embodiments, FCC catalyst includes at least about 5wt.% barium ions.In some embodiments, FCC catalyst Including about 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,2,3,4,5,6,7,8,9 or 10wt.% (including wherein increment) barium Ion.In some embodiments, FCC catalyst includes about 0.3wt.% to about 5wt.% barium ions.In some embodiments, FCC catalyst includes about 2wt.% to about 5wt.% barium ions.In some embodiments, FCC catalyst is arrived including about 2wt.% About 4wt.% barium ions.

In some embodiments, Y- zeolites have and are less than or equal toCell parameter.In some embodiments, Y- zeolites, which have, to be less than or equal toCell parameter.In some embodiments, Y- zeolites have and are less than or equal toCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites With aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites With aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites With aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have Have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have Have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have Have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter. In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have Have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have aboutTo aboutCell parameter.In some embodiments, Y- zeolites have about 24.10,24.11,24.12,24.13,24.14, 24.15、24.16、24.17、24.18、24.19、24.20、24.21、24.22、24.23、24.24、24.25、24.26、 24.27、24.28、24.29、24.30、24.31、24.32、24.33、24.34、24.35、24.36、24.37、24.38、 24.39、24.40、24.41、24.42、24.43、24.44、24.45、24.46、24.47、24.48、24.49、24.50、 24.51、24.52、24.53、24.54、24.55、24.56、24.57、24.58、24.59、24.60、24.61、24.62、 24.63,24.64,24.65,24.66,24.67,24.68,24.69 orCell parameter.

In some embodiments, the microspherical catalyst disclosed herein for including about 3.3wt.% barium ions, wherein catalyst With the phase including about 18wt.% zeolites, about 30wt.% mullites, about 2wt.% anatases and about 50wt.% amorphous materials Composition.In some embodiments, zeolite has aboutCell parameter.In some embodiments, catalyst is handed in ion Change place III, which is in zeolite unit cell, contains about 4 barium atoms.In some embodiments, the score seat of ion exchange site III Mark is x=y=0.35 and z=0.21.In some embodiments, by x-ray diffraction, only about half of barium ions can be located at In zeolite.In some embodiments, the average particle size of catalyst is 60-80 microns.

In some embodiments, the microspherical catalyst disclosed herein for including about 3.3wt.% barium ions, wherein catalyst With including about 18wt.%Y- zeolites, about 30wt.% mullites, about 2wt.% anatases and about 50wt.% amorphous materials Phase composition.In some embodiments, Y- zeolites have aboutCell parameter.In some embodiments, catalyst from Son, which exchanges position III and is in Y- zeolite unit cells, contains about 4 barium atoms.In some embodiments, ion exchange site III Score coordinate is x=y=0.35 and z=0.21.In some embodiments, by X-ray diffraction, only about half of barium ions can To be located in zeolite.In some embodiments, the average particle size of catalyst is 60-80 microns.

In some embodiments, microspherical catalyst disclosed herein has the zeolite substantially exchanged by barium, mullite With the phase composition of amorphous material composition.In some embodiments, microspherical catalyst disclosed herein has substantially by barium The phase composition of the zeolite, mullite, anatase and amorphous material composition of exchange.In some embodiments, disclosed herein micro- Sphere catalyst has zeolite, the about 20wt.% to about 35wt.% substantially exchanged to about 50wt.% barium by about 10wt.% The phase composition that mullite, about 1wt.% are formed to about 5wt.% anatases and about 25wt.% to about 55wt.% amorphous materials, Wherein catalyst contains about 2wt.% to about 10wt.% barium ions.In some embodiments, microspherical catalyst disclosed herein, There is the phase composition that the Y- zeolites, mullite, anatase and the amorphous material that are substantially exchanged by barium form, wherein zeolite to exist for it Crystallization is layer on the surface of porous alumina-containing matrix.

In some embodiments, microspherical catalyst disclosed herein has the Y- zeolites substantially exchanged by barium, Mo Lai The phase composition of stone and amorphous material composition.In some embodiments, microspherical catalyst disclosed herein, have substantially by The phase composition of Y- zeolites, mullite, anatase and amorphous material composition that barium exchanges.In some embodiments, public herein Microspherical catalyst is opened, has the Y- zeolites substantially exchanged to about 50wt.% barium by about 10wt.%, about 20wt.% to about 35wt.% mullites, about 1wt.% are formed to about 5wt.% anatases and about 25wt.% to about 55wt.% amorphous materials Phase composition, wherein catalyst contain about 2wt.% to about 10wt.% barium ions.In some embodiments, microballoon disclosed herein Catalyst has the phase composition that the Y- zeolites, mullite, anatase and the amorphous material that are substantially exchanged by barium form, It is layer that middle Y- zeolites crystallize on the surface of porous alumina-containing matrix.

Preparation method

In another aspect, the method disclosed herein for preparing FCC catalyst described herein.

The method for preparing microballoon fluidized catalytic cracking catalyst may include microsphere is made to mix with barium solution micro- to form barium- Sphere mixture；With calcining barium-microsphere mixture to form the first calcined materials, wherein before being mixed with barium solution, it is micro- Sphere includes the zeolite that crystallization is layer on the surface of porous alumina-containing matrix.In some embodiments, barium is replaced using caesium.

The method for preparing microballoon fluidized catalytic cracking catalyst may include microsphere is made to mix with barium solution micro- to form barium- Sphere mixture；With calcining barium-microsphere mixture to form the first calcined materials, wherein before being mixed with barium solution, it is micro- Sphere includes the Y- zeolites that crystallization is layer on the surface of porous alumina-containing matrix.In some embodiments, it is replaced using caesium Barium.

In some embodiments, it is mixed under acidic pH.In some embodiments, in about pH=5 or pH It is mixed under=5.In some embodiments, it is at least mixed at pH=5.In some embodiments, in about pH=4 or It is mixed under pH=4.In some embodiments, it is at least mixed at ph=4.5.In some embodiments, in about pH=3 Or it is mixed under pH=3.In some embodiments, it is at least mixed at pH=3.In some embodiments, in about pH It is mixed under=2.5 or pH=2.5.In some embodiments, it is at least mixed at pH=2.5.In some embodiments In, it is mixed at pH=2 or about pH=2.In some embodiments, it is at least mixed at pH=2.

In some embodiments, it is mixed at a temperature below the room temperature.In some embodiments, it carries out at room temperature Mixing.In some embodiments, it is mixed at temperatures greater than room temperature.In some embodiments, at least about 50 DEG C At a temperature of mixed.In some embodiments, it is mixed at a temperature of at least about 60 DEG C.In some embodiments, exist It is mixed at a temperature of at least about 70 DEG C.In some embodiments, it is mixed at a temperature of at least about 80 DEG C.At some In embodiment, in about 10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95 or 100 DEG C of temperature It is mixed under degree (including wherein increment).

In some embodiments, calcining is carried out at least about 15 minutes.In some embodiments, calcining is carried out at least about 30 minutes.In some embodiments, calcining is carried out at least one hour.In some embodiments, calcining is carried out at least about two Hour.In some embodiments, calcining is carried out about one to about two hours.Calcining in some embodiments, is carried out about 0.25, 0.5,1,2,3,4 or 5 hour, including wherein increment.

In some embodiments, calcining carries out at a temperature of about 500 DEG C to about 750 DEG C.In some embodiments, it calcines It is carried out at a temperature of about 480 DEG C to about 740 DEG C.In some embodiments, at a temperature of calcining is up to about 650 DEG C at about 500 DEG C It carries out.In some embodiments, calcining carries out at a temperature of about 600 DEG C to about 700 DEG C.In some embodiments, calcining exists About 480,500,525,550,575,600,625,650,675,700,725,750,775,800,825 or 850 DEG C of temperature (packet Include wherein increment) under carry out.

Method can further comprise before being mixed with barium solution, and microsphere is made to be mixed with ammonium salt solution, wherein molten with ammonium Microsphere includes the Y- zeolites in na form before liquid mixing.In some embodiments, it is blended in acid ph value with ammonium salt solution Under the conditions of carry out.In some embodiments, it is carried out with being blended under pH=5 for ammonium salt solution.In some embodiments, with ammonium salt solution Be blended under about pH=5 and carry out.In some embodiments, it is at least carried out at pH=5 with the mixing of ammonium salt solution.In some realities It applies in example, the mixing with ammonium salt solution carries out at ph=4.5.In some embodiments, with ammonium salt solution be blended under about pH=4 into Row.In some embodiments, it is at least carried out at ph=4.5 with the mixing of ammonium salt solution.In some embodiments, mixed with ammonium salt solution Conjunction is carried out at pH=3.In some embodiments, it is carried out with being blended under about pH=3 for ammonium salt solution.In some embodiments, Mixing with ammonium salt solution is at least carried out at pH=3.In some embodiments, it is carried out with being blended under pH=2.5 for ammonium salt solution. In some embodiments, it is carried out with being blended under about pH=2.5 for ammonium salt solution.In some embodiments, with the mixing of ammonium salt solution At least carried out at pH=2.5.In some embodiments, it is carried out with being blended under pH=2 for ammonium salt solution.In some embodiments In, it is carried out with being blended under about pH=2 for ammonium salt solution.In some embodiments, with the mixing of ammonium salt solution at least at pH=2 into Row.In some embodiments, it is carried out at temperatures greater than room temperature with the mixing of ammonium salt solution.In some embodiments, molten with ammonium Liquid be blended at least about 50 DEG C at a temperature of carry out.In some embodiments, at least about 60 DEG C are blended in ammonium salt solution At a temperature of carry out.In some embodiments, with ammonium salt solution be blended at least about 70 DEG C at a temperature of carry out.In some embodiments In, (including wherein increase with the temperature for being blended in about 50,55,60,65,70,75,80,85,90,95 or 100 DEG C of ammonium salt solution Amount) under carry out.In some embodiments, barium solution is replaced using caesium solution.

Method can further comprise that the first calcined materials is made to mix with another ammonium salt solution to form ammonification material.In some realities It applies in example, is carried out with being blended under acidic pH for another ammonium salt solution.In some embodiments, mixed with another ammonium salt solution Conjunction is carried out at pH=5.In some embodiments, it is carried out with being blended under about pH=5 for another ammonium salt solution.In some embodiments In, the mixing with another ammonium salt solution is at least carried out at pH=5.In some embodiments, it is blended in pH with another ammonium salt solution =4 times progress.In some embodiments, it is carried out with being blended under about pH=4 for another ammonium salt solution.In some embodiments, with The mixing of another ammonium salt solution at least carries out at ph=4.5.In some embodiments, it is blended under pH=3 with another ammonium salt solution It carries out.In some embodiments, it is carried out with being blended under about pH=3 for another ammonium salt solution.In some embodiments, with another ammonium The mixing of solution is at least carried out at pH=3.In some embodiments, it is carried out with being blended under pH=2.5 for another ammonium salt solution. In some embodiments, it is carried out with being blended under about pH=2.5 for another ammonium salt solution.In some embodiments, molten with another ammonium The mixing of liquid is at least carried out at pH=2.5.In some embodiments, it is carried out with being blended under pH=2 for another ammonium salt solution. In some embodiments, carried out with being blended under about pH=2 for another ammonium salt solution.In some embodiments, with another ammonium salt solution Mixing is at least carried out at pH=2.

In some embodiments, it is carried out at a temperature below the room temperature with the mixing of ammonium salt solution.In some embodiments, exist It is mixed at room temperature.In some embodiments, it is mixed at temperatures greater than room temperature.In some embodiments, extremely It is mixed at a temperature of about 50 DEG C few.In some embodiments, it is mixed at a temperature of at least about 60 DEG C.In some realities It applies in example, is mixed at a temperature of at least about 70 DEG C.In some embodiments, it is mixed at a temperature of at least about 80 DEG C It closes.In some embodiments, about 10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95 or It is mixed at 100 DEG C of temperature (including wherein increment).

Method can further comprise calcining ammonification material to form the second calcined materials.In some embodiments, ammonia is calcined Change material to carry out at least about 15 minutes.In some embodiments, calcining ammonification material carries out at least about 30 minutes.In some implementations In example, calcining ammonification material carries out at least about one hour.In some embodiments, it is small to carry out at least about two for calcining ammonification material When.In some embodiments, calcining ammonification material carries out about one to about two hours.In some embodiments, ammonification material is calcined Carry out about 0.25,0.5,0.75,1,2,3,4 or 5 hour, including wherein increment.In some embodiments, calcining ammonification material exists It is carried out at a temperature of about 500 DEG C to about 800 DEG C.In some embodiments, calcining ammonification material is at about 500 DEG C to about 700 DEG C At a temperature of carry out.In some embodiments, calcining ammonification material carries out at a temperature of about 500 DEG C to about 600 DEG C.In some realities It applies in example, calcining ammonification material carries out at a temperature of about 600 DEG C to about 700 DEG C.In some embodiments, calcining about 500, 525,550,575,600,625,650,675,700,725,750,775,800,825,850 DEG C of temperature (including wherein increment) Lower progress.

Method further comprises steam treatment.In some embodiments, steam treatment is carried out to the first calcined materials.One In a little embodiments, steam treatment is carried out to the second calcined materials.In some embodiments, at a temperature of at least about 600 DEG C into Row steam treatment.In some embodiments, steam treatment is carried out at a temperature of at least about 700 DEG C.In some embodiments, exist Steam treatment is carried out at a temperature of at least about 800 DEG C.In some embodiments, it is carried out at a temperature of about 600 DEG C to about 800 DEG C Steam treatment.In some embodiments, steam treatment is carried out at a temperature of about 600 DEG C to about 700 DEG C.In some embodiments In, carry out steam treatment at a temperature of about 700 DEG C to about 800 DEG C.In some embodiments, about 600,625,650,675, 700, steam treatment is carried out at 725,750,775,800,825 or 850 DEG C of temperature (including wherein increment).In some embodiments In, steam treatment is carried out at least about two hours.In some embodiments, steam treatment is carried out at least about three hours.One In a little embodiments, steam treatment is carried out at least about four hours.In some embodiments, steam treatment is carried out about one to about four Hour.In some embodiments, steam treatment is carried out about two to about four hours.In some embodiments, by steam treatment into Row about 1,2,3,4,5,6,7,8,9 or 10 hour, including wherein increment.In some embodiments, final step is anti-in fluid bed It answers in device and carries out.In some embodiments, final step carries out in rotary calcining stove.

In some embodiments, the method for preparing microballoon fluidized catalytic cracking catalyst substantially comprises the steps of： Microsphere is set to be mixed with barium solution to form barium-microsphere mixture；Barium-microsphere mixture is calcined to form the first calcining material Material；The first calcined materials are made to be mixed with ammonium salt solution to form ammonification material；Ammonification material is calcined to form the second calcined materials；With And the second calcined materials of steam treatment.In some embodiments of method, microsphere includes zeolite.In some embodiments of method In, microsphere includes the Y- zeolites that crystallization is layer on the surface of porous alumina-containing matrix.In the other embodiments of method, Before mixing, microsphere is preprocessed to exchange sodium with ammonium ion.In some embodiments, barium is replaced using caesium.

In some embodiments of method, before being mixed with barium solution and carrying out second of calcining and steam treatment, packet The microsphere for including zeolite undergoes the mixing in ammonium salt solution and calcines for the first time.In the other embodiments of method, for the first time Microsphere is set to be mixed with the second ammonium salt solution after calcining.In some embodiments of method, barium is replaced using caesium.

In some embodiments of method, before being mixed with barium solution and carrying out second of calcining and steam treatment, packet The microsphere for including on the surface of porous alumina-containing matrix the Y- zeolites that crystallization is layer undergoes mixing in ammonium salt solution and the Primary calcining.In the other embodiments of method, microsphere is set to be mixed with the second ammonium salt solution after first time calcining.At some In embodiment, barium is replaced using caesium.

In another aspect, the microballoon FCC catalysis disclosed herein such as prepared by any method disclosed herein Agent.

Application method

In another aspect, the method disclosed herein that butylene is generated in FCC system, wherein the method includes using FCC catalyst described herein.

In another aspect, the method disclosed herein for improving the butylene yield in FCC system, wherein the method includes Use FCC catalyst described herein.

In another aspect, the method disclosed herein for improving the butylene selectivity in FCC system, wherein the method packet It includes and uses FCC catalyst described herein.

In another aspect, the method disclosed herein for reducing the coke production rate in FCC system, wherein the method packet It includes and uses FCC catalyst described herein.

In another aspect, the method disclosed herein for reducing the hydride metastasis tendency in FCC system, wherein the side Method includes using FCC catalyst described herein.

Therefore the present invention of general description will be better understood with reference to following instance, the example be in order to illustrate rather than Limitation is of the invention and provides.

Example

Material and method

Sodium will be containedAs initial substance.Barium nitrate solution is made by crystalline material.At 1150 °F Under in still air using be added to solid calcining charging 25% liquid water by laboratory calcining carry out two hours.It will contain The angle of ordered pair and the X ray diffracting data collection of intensity data are converted into Analysis of Currency Structure system (General Structure Analysis System；GSAS) form and then use by EXPGui (graphic user interface of GSAS) drive GSAS carry out Rietveld refine.The instrumental function of X-ray diffractometer uses NIST SRM 660b LaB₆Sample determines.Make Wire shaped is modeled with 2 type of profile function；Background can use 1 type of function or 6 types to model.The usage of these profiles and background function by Larson and Von Dreele exist《Analysis of Currency Structure system (General Structure Analysis System) (GSAS)》, Los Alamos National laboratory reports LAUR 86-748, discussed in 2004.Decatize is in open type steaming boiler In 100% steam in carried out in a fluidized bed four hours under 1500 °F.Use ACE^TM1 reactor, wax oil charging, 2.125 " Syringe height catalytic cracking result is obtained under about 1020 °F (548 DEG C).

The exemplary preparation containing titanate catalyst of example 1.

It manufactures microsphere and uses and retouched in the US 6656347 being incorporated herein by reference in its entirety by Stockwell The method stated carries out Y- crystallization of zeolites.Referred to asResulting materials contain the Y- zeolites in na form.With It is swapped afterwards with ammonium nitrate (3,80 DEG C of pH) and then uses barium nitrate solution exchange material.Material through filtering, drying and 621 DEG C are calcined two hours.Material then uses ammonium nitrate (3,80 DEG C of aqueous suspensions of pH) to exchange again, filtering, dry and again It is calcined two hours at 621 DEG C.Barium amount in catalyst is changed by changing concentration of the barium in barium nitrate solution.Through twice The catalyst of calcining is then deactivated at 815 DEG C 4 hours and then in ACE in a fluidized bed reactor with 100% steam^TMInstead It answers and uses air stream constant time scheme evaluation in device.

The research of 2. zeolite stability of example

Using the program in example 1 byIntermediate product is made two groups and containsMaterial.The barium content range of first group of material is 0.2wt.% to 1.0wt.%.Following article will be discussed It states, these first materials is made to become finished product and in ACE^TMIts catalysis characteristics is assessed in reactor.Second group of material is then with increase Barium content be made.Observe that Ba at least makes Y- zeolites unstable when being exchanged from nitrate solution.As barium content increases, steam Unit cell dimension processed and steam zeolite surface area (zeolite surface area；ZSA it) all reduces, as shown in figs. 1 and 2.To the greatest extent Barium in pipe zeolite occurs not in the form of BaO, but counts purpose for experiment, and barium is in Fig. 1, Fig. 2 and Fig. 5-9 in the form of BaO It lists.The known stabilization for the Y zeolite unit cell sizes that illustration displaying in Fig. 1 is realized by lanthanum.Illustration displaying in Fig. 2 and business material Expect it is consistent, laboratory manufacture contain lanthanum Steam ZSA and oxygen Change lanthanum content constant.Behavior shown in Fig. 2：Make the increase of barium content, ZSA reduce with to alkali metal, as sodium it is contemplated that On the same direction.It is apparent that barium is to fluxing and destroying zeolite has appropriateness active.

Barium and lanthanum do not make substrate surface area stablize, as shown in Figure 3.Substrate surface area displaying is steamed with barium monoxide or oxygen The trend changed the increase of lanthanum content and reduced.This is unexpected.Containing mullite, Y- zeolites and through engineering The spinelle of transformation.Engineered spinels is similar to γ-Al₂O₃And stablized by silica.Known lanthana and oxygen Both changing barium makes transitional alumina stablize, from the surface area losses caused by High-temperature water heat treatment.Rather low decatize temperature Degree (1500 °F/815 DEG C) is less likely to cause engineered spinelle loss exhibiting high surface product.AboutMost substrate surface areas are related to zeolite rather than matrix spinelle.Following facts：Ba and La exist Substrate surface area is not all set to stablize most of and matrix alumina or the mullite for showing this " matrix " strongly in 815 DEG C of decatizes It is completely uncorrelated, but it is related to outer surface of zeolite.Basic dopant including barium monoxide and lanthana is showed with fusing The tendency of zeolite perimeter.

Example 4. is zeolite structured

Using X-ray diffraction combination Rietveld analyses 3.3wt.% is selected for more detailed structure featureCatalyst.This material of conventional x-ray diffraction character report contains Y- zeolites, mullite and sharp Titanium ore.GSAS refine obtains at convergenceY- zeolite unit cell parameters estimation, this with use ASTM Method D3942The result of acquisition is well consistent.It is because data use the examination of GSAS refine to think occurrence difference Sample is through hydration, and data are hydrated based on the method D3942 samples analyzed according to method.Rietveld refine can provide sample The estimation of the mass fraction of product crystalline portion but non-direct quantitative amorphous material.Previous refine work causes to use these materials The estimation of the anatase content of the 1.72wt.% of material.Know that the anatase content of sample is about 1.72wt.%, and it was found that this The apparent anatase mass fraction of a sample is 3.91wt.%, estimates the mass fraction of mullite and Y zeolites.From zeolite surface The mass fraction of product estimation zeolite.Estimate that the micro pore surface area of in-situ Y zeolite is about 660m²/g.Micro pore surface area is bent using T Difference between BET surface area and external surface area that line method measures.This estimation can be additionally used in the matter for estimating Y zeolites in sample Amount divides rate：Micro pore surface area/660=such as passes through the mass fraction of BET Estimation and Measurements.Also its of estimation zeolite mass fraction is used Its method：So-called ZI (Zeolite Index) based on ASTM method D3906, although this method exists just in the presence of mullite Biasing.Using these methods, three kinds of estimated values of zeolite content are obtained：ZI, 25wt.%；BET, 19wt.%；And Rietveld, 16wt.%.

In view of known biasing, it is reasonable to which ZI estimates highest：It should not trust.BET and Rietveld estimations good one It causes.Rietveld is analysis shows mullite content is 26wt.%.Rietveld analyses, which also indicate that, steams 3.3wt.%56wt.% be it is amorphous.It is SiO to be included in this amorphous material₂Stable γ--Al₂O₃Spinelle, the spinel diffraction are excessively weak so that can not be detected in this experiment.

Finally, the position of assessment barium ions is analyzed using Rietveld.Rietveld refine announcement steamsIn lanthanum occupy position I ' in sodalite cage and II '.In steaming without any exchange cationIn, it is found that aluminium appears in these positions.In crystallizationIn, sodium occurs In position II and III in supercage and in position I ' and II '.These find all consistent with document observation result.

The refine that I ', II ', the barium at the positions II and III occupy is carried out respectively and together.This analysis shows position I ', Barium at II ' and II occupies to bear.Certainly, this is physically impossible and shows that barium does not appear in those positions.Meaning Other places, position III refine is to slightly just occupying.Low occupation rate can correspond to considerable barium, although because the weight of position III Number is 96.Refine shows about 1/3 of whole barium in catalyst present in the position III in Y- zeolites.This is equivalent in vapour About 6wt.%Ba after steaming in remaining zeolite.Notably, previously the Ba of not yet reported position III is occupied.Y- zeolites Be reflected in this refine model it is very good.Many refine fitting parameters are extremely good.As a result show that most of barium do not exist In zeolite.It is flowed in the presence of the steam that known barium hydroxide can be at high temperature.(815 DEG C) foots of steam temperature in these experiments Enough height are so that movement may occur.Most barium may have occurred on silica-alumina amorphous material rather than Y- On zeolite.

5. catalysis characteristics of example

Have shown that barium instead of lanthanum ion exchange toY- zeolites cause it is very different physico Consequence is learned, is studied in ACE^TMThe catalytic result obtained in reactor.

ContainActivity be less than analog containing La.Fig. 4 illustrates for coming from two ACE^TMActivity Result under catalyst/oil (C/O)=5 second order activity.For each ACE^TMTwo kinds of lanthanas control of experiment is actually It is the material for the same type for undergoing identical steaming condition.Those controls show the activity from a movable result than another Movable result is high by about 9%.The activity that this activity difference over time does not influence to aoxidize titanate catalyst is less than lanthana The observed result of catalyst.But activity difference does not make the activity of oxidation titanate catalyst higher than wherein unused metal cation The activity of catalyst is indefinite.In Fig. 4, wherein being labeled as " aluminium oxide " without the catalyst that metal cation exchanges.This " oxygen The activity of change aluminium " material is less than all materials containing barium monoxide.On the other hand, " aluminium oxide " material assessed in another experiment Activity is slightly above all materials containing barium monoxide.Therefore, it is still not clear containing BaActivity whether higher than not Containing dopant

The catalyst that Fig. 5 displaying barium contents are 0.7-1.1wt.% has and 1.2wt.%La₂O₃Comparative catalyst is similar Gasoline selective.3.5wt.% lanthanas control (not shown) is made compares more about 1% gasoline than 1.2wt.% lanthana. It is generated about gasoline, these titanate catalysts containing oxidation are obviously not better than the reference of 3wt.% lanthanas.Compared to 1.2wt.% oxygen Change lanthanum control, on a relative basis, these catalyst containing barium monoxide are made more 0.4% to few 0.2% coke.These are containing low The catalyst of barium monoxide has and 1.2wt.%Comparable coke selectivity.

Also performance of the assessment with higher oxygen barium content.The selection gasoline yield result of this experiment is showed in Fig. 6. In this experiment, lanthanum oxide catalyst is expressively relatively preferable.For example, 3.3wt.%It compares In 3.5wt.%Reduction with 2wt.% gasoline yields.Oxidation titanate catalyst, which also has, to be worse than Or similar to the gasoline selective (not shown) without barium monoxide and the catalyst of lanthana.On the other hand, containing barium monoxide Catalyst manufactures less coke (referring to Fig. 7).The coke ratio 3.5wt.% of catalyst manufacture containing 3.3wt.% barium monoxideFew about 12%.However, under lower barium monoxide content, coke advantage is not observed.These realities It tests when showing maximum coke benefit to appear in barium monoxide content being about 3wt.%, this kind of catalyst ratio does not have exchange cation Catalyst manufacture more 0.3-0.6wt.% gasoline and few about 7wt.% coke.

Also assess totality LPG productivities.In addition, the GC data obtained from these ACE experiments make it possible to assess olefinicity. Fig. 8 shows 1.2 or 3.5wt.% of 2-3wt.% oxidation titanate catalyst manufacture ratiosMore LPG.To the greatest extent Pipe does not have barium monoxide has similar LPG advantages with the catalyst of lanthana, but catalyst manufacture is catalyzed than barium monoxide The more coke of agent.

Catalyst containing barium monoxide shows ratioMuch higher isobutene/iso-butane ratio, such as Shown in Fig. 9.Than the higher isobutyl of catalyst without Ba and La as exchange cation Alkene/isobutene ratio.Isobutene/isobutene ratio diagnoses hydride transition intensity.Aoxidizing titanate catalyst has rather low hydrogen Compound transfer ability.Oxidation titanate catalyst manufactures the positive fourth of more propylene, ethylene and Duo Yue 0.8-1% than lanthanum oxide catalyst Alkene.These consider that oxidation titanate catalyst is all supported to manufacture asserting for more olefin products.

A kind of microballoon fluidized catalytic cracking catalysts of paragraph A., including Y- zeolites and barium ions.

The average particle size of catalyst of the paragraph B. according to paragraph A, wherein catalyst is about 60 to about 100 microns.

The average particle size of catalyst of the paragraph C. according to paragraph A or paragraph B, wherein catalyst is about 60 to about 80 micro- Rice.

The average particle size of catalyst of the paragraph D. according to paragraph A or paragraph B, wherein catalyst is about 70 to about 90 micro- Rice.

Catalyst of the paragraph E. according to any one of paragraph A to D, wherein catalyst have comprising at least about The phase composition of 10wt.%Y- zeolites.

Catalyst of the paragraph F. according to any one of paragraph A to D, wherein catalyst have comprising at least about The phase composition of 15wt.%Y- zeolites.

Catalyst of the paragraph G. according to any one of paragraph A to D, wherein catalyst have comprising at least about The phase composition of 18wt.%Y- zeolites.

Catalyst of the paragraph H. according to any one of paragraph E to G, wherein phase composition further include at least about 30wt.% amorphous materials.

Catalyst of the paragraph I. according to any one of paragraph E to G, wherein phase composition further include at least about 40wt.% amorphous materials.

Catalyst of the paragraph J. according to any one of paragraph E to G, wherein phase composition further include at least about 50wt.% amorphous materials.

Catalyst of the paragraph K. according to any one of paragraph H to J, wherein amorphous material include silica-oxygen Change aluminium.

Catalyst of the paragraph L. according to any one of paragraph E to K, wherein phase composition further include at least about 20wt.% mullites.

Catalyst of the paragraph M. according to any one of paragraph E to K, wherein phase composition further include at least about 30wt.% mullites.

Catalyst of the paragraph N. according to any one of paragraph A to M, wherein Y- zeolites have aboutTo aboutCell parameter.

Catalyst of the paragraph O. according to any one of paragraph A to N, wherein Y- zeolites have aboutTo aboutCell parameter.

Catalyst of the paragraph P. according to any one of paragraph A to O, wherein Y- zeolite unit cells are in ion exchange site It include barium ions at III.

Catalyst of the paragraph Q. according to any one of paragraph A to P, wherein Y- zeolite unit cells are in ion exchange site Include 4 barium atoms at III.

Catalyst of the paragraph R. according to any one of paragraph A to Q, wherein by x-ray diffraction, no more than about half Barium ions can be located on Y- zeolites.

Catalyst of the paragraph S. according to any one of paragraph A to R, wherein barium ions do not occupy Y- zeolite unit cells Ion exchange site I ' and II '.

Catalyst of the paragraph T. according to any one of paragraph A to S, wherein catalyst include at least about 2wt.% barium from Son.

Catalyst of the paragraph U. according to any one of paragraph A to T, wherein catalyst include at least about 3wt.% barium from Son.

Catalyst of the paragraph V. according to any one of paragraph A to U, wherein Y- zeolites are in porous alumina-containing matrix Crystallization is layer on surface.

Catalyst of the paragraph W. according to paragraph V, mesostroma derive from the kaolin calcined by heat release.

A kind of microspherical catalysts including about 3.3wt.% barium ions of paragraph X., wherein the catalyst has comprising about The phase composition of 18wt.%Y- zeolites, about 30wt.% mullites, about 2wt.% anatases and about 50wt.% amorphous materials.

Catalyst of the paragraph Y. according to paragraph X, wherein Y- zeolites have aboutCell parameter.

Catalyst of the paragraph Z. according to paragraph X or paragraph Y, wherein the catalyst is at ion exchange site III Y zeolite unit cells in contain about 4 barium atoms.

Catalyst of the paragraph AA. according to paragraph Z, the wherein score coordinate of ion exchange site III is x=y= 0.35 and z=0.21.

Catalyst of the paragraph AB. according to any one of paragraph X to AA, wherein by x-ray diffraction, only about half barium Ion can be located in zeolite.

Catalyst of the paragraph AC. according to any one of paragraph X to AB, the wherein average particle size of catalyst are 60-80 Micron.

A kind of methods preparing microballoon fluidized catalytic cracking catalyst of paragraph AD., the method include：

Microsphere is set to be mixed with barium solution to form barium-microsphere mixture；With

Barium-the microsphere mixture is calcined to form the first calcined materials；

Wherein：

Before being mixed with the barium solution, the microsphere is included in crystallization on the surface of porous alumina-containing matrix and is The Y- zeolites of layer.

Methods of the paragraph AE. according to paragraph AD, wherein being carried out with being blended under acidic pH for barium solution.

Methods of the paragraph AF. according to paragraph AD or paragraph AE, wherein being carried out with being blended under pH=3 for barium solution.

Methods of the paragraph AG. according to any one of paragraph AD to AF, wherein being blended in higher than room temperature with barium solution At a temperature of carry out.

Methods of the paragraph AH. according to any one of paragraph AD to AG, wherein being blended at least about 50 with barium solution It is carried out at a temperature of DEG C.

Methods of the paragraph AI. according to any one of paragraph AD to AG, wherein being blended in about 80 DEG C with barium solution At a temperature of carry out.

Methods of the paragraph AJ. according to any one of paragraph AD to AI, wherein calcining barium-microsphere mixture carry out to It is about 15 minutes few.

Methods of the paragraph AK. according to any one of paragraph AD to AI, wherein calcining barium-microsphere mixture carry out to It is about one hour few.

Methods of the paragraph AL. according to any one of paragraph AD to AI, wherein calcining barium-microsphere mixture carry out to It is about two hours few.

Methods of the paragraph AM. according to any one of paragraph AD to AL, wherein calcining barium-microsphere mixture is about It is carried out at a temperature of 500 DEG C to about 700 DEG C.

Methods of the paragraph AN. according to any one of paragraph AD to AM, is further contained in before being mixed with barium solution Microsphere is set to be mixed with ammonium salt solution, wherein microsphere includes the Y- zeolites in na form before being mixed with ammonium salt solution.

Methods of the paragraph AO. according to paragraph AN, wherein being carried out with being blended under acidic pH for ammonium salt solution.

Methods of the paragraph AP. according to paragraph AN or paragraph AO, wherein being carried out with being blended under pH=3 for ammonium salt solution.

Methods of the paragraph AQ. according to any one of paragraph AN to AP, wherein being blended in higher than room temperature with ammonium salt solution At a temperature of carry out.

Methods of the paragraph AR. according to any one of paragraph AN to AQ, wherein being blended at least about 50 with ammonium salt solution It is carried out at a temperature of DEG C.

Methods of the paragraph AS. according to any one of paragraph AN to AQ, wherein being blended in about 80 DEG C with ammonium salt solution At a temperature of carry out.

Methods of the paragraph AT. according to any one of paragraph AN to AS, further include make the first calcined materials with it is another One ammonium salt solution is mixed to form ammonification material.

Methods of the paragraph AU. according to paragraph AT, wherein with another ammonium salt solution be blended under acidic pH into Row.

Methods of the paragraph AV. according to paragraph AT or paragraph AU, wherein with another ammonium salt solution be blended under pH=3 into Row.

Methods of the paragraph AW. according to any one of paragraph AT to AV, wherein being higher than with being blended in for another ammonium salt solution It is carried out at a temperature of room temperature.

Methods of the paragraph AX. according to any one of paragraph AT to AW, wherein being blended at least with another ammonium salt solution It is carried out at a temperature of about 50 DEG C.

Methods of the paragraph AY. according to any one of paragraph AT to AW, wherein being blended in about 80 with another ammonium salt solution It is carried out at a temperature of DEG C.

Methods of the paragraph AZ. according to any one of paragraph AT to AY further includes calcining ammonification material to be formed Second calcined materials.

Methods of the paragraph BA. according to paragraph AZ, wherein calcining ammonification material carries out at least about 15 minutes.

Methods of the paragraph BB. according to paragraph AZ, wherein calcining ammonification material carries out at least about one hour.

Methods of the paragraph BC. according to paragraph AZ, wherein calcining ammonification material carries out at least about two hours.

Methods of the paragraph BD. according to any one of paragraph AZ to BC, wherein calcining ammonification material arrives about at about 500 DEG C It is carried out at a temperature of 700 DEG C.

Methods of the paragraph BE. according to any one of paragraph AD to BD, further includes steam treatment.

Methods of the paragraph BF. according to paragraph BE, wherein steam treatment carry out at a temperature of at least about 600 DEG C.

Methods of the paragraph BG. according to paragraph BE, wherein steam treatment carry out at a temperature of at least about 700 DEG C.

Methods of the paragraph BH. according to paragraph BE, wherein steam treatment carry out at a temperature of at least about 800 DEG C.

Methods of the paragraph BI. according to any one of paragraph BE to BH, wherein steam treatment carry out at least about two hours.

Methods of the paragraph BJ. according to any one of paragraph BE to BH, wherein steam treatment carry out at least about three hours.

Methods of the paragraph BK. according to any one of paragraph BE to BH, wherein steam treatment carry out at least about four hours.

Methods of the paragraph BL. according to any one of paragraph BE to BK, wherein steam treatment are in a fluidized bed reactor It carries out.

Paragraph BM. is a kind of as passed through the microballoon fluidized catalytic cracking catalyst prepared by any one of paragraph AD to BL.

A kind of microballoon fluidized catalytic cracking catalysts of paragraph BN., including Y- zeolites and barium ions.

Catalyst of the paragraph BO. according to paragraph BN, wherein the average particle size of the catalyst is about 60 to about 100 micro- Rice or about 60 to about 80 microns or about 70 to about 90 microns.

Catalyst of the paragraph BP. according to paragraph BN or paragraph BO, wherein catalyst, which have, includes at least about 10wt.% The phase composition of Y- zeolites or at least about 15wt.%Y- zeolites or at least about 18wt.%Y- zeolites.

It is amorphous to further include at least about 30wt.% for catalyst of the paragraph BQ. according to paragraph BP, wherein phase composition Material or at least about 40wt.% amorphous materials or at least about 50wt.% amorphous materials.

Catalyst of the paragraph BR. according to paragraph BQ, wherein amorphous material include silica-alumina.

Catalyst of the paragraph BS. according to any one of paragraph BP to BR, wherein phase composition further include at least about 20wt.% mullites or at least about 30wt.% mullites.

Catalyst of the paragraph BT. according to any one of paragraph BN to PS, wherein Y- zeolites have aboutTo aboutOr aboutTo aboutCell parameter.

Catalyst of the paragraph BU. according to any one of paragraph BN to BT, wherein Y- zeolite unit cells are in ion-exchange sites Set at III includes barium ions.

Catalyst of the paragraph BV. according to any one of paragraph BN to BU, wherein Y- zeolite unit cells are in ion-exchange sites Set at III includes 4 barium atoms.

Catalyst of the paragraph BW. according to any one of paragraph BN to BV, wherein by x-ray diffraction, no more than about Half barium ions can be located on Y- zeolites.

It is brilliant that catalyst of the paragraph BX. according to any one of paragraph BN to BW, wherein barium ions do not occupy Y- zeolites The ion exchange site I ' and II ' of born of the same parents.

Catalyst of the paragraph BY. according to any one of paragraph BN to BX, wherein catalyst include at least about 2wt.% Barium ions or at least about 3wt.% barium ions.

Catalyst of the paragraph BZ. according to any one of paragraph BN to BY, wherein Y- zeolites are in porous salic base Crystallization is layer on the surface of matter.

Catalyst of the paragraph CA. according to paragraph BZ, mesostroma derive from the kaolin calcined by heat release.

A kind of microspherical catalysts including about 3.3wt.% barium ions of paragraph CB., wherein the catalyst has comprising about The phase composition of 18wt.%Y- zeolites, about 30wt.% mullites, about 2wt.% anatases and about 50wt.% amorphous materials.

Catalyst of the paragraph CC. according to paragraph CB, wherein Y- zeolites have aboutCell parameter.

Catalyst of the paragraph CD. according to paragraph CB or paragraph CC, wherein the catalyst is in ion exchange site III Contain about 4 barium atoms in the Y zeolite unit cells at place.

Catalyst of the paragraph CE. according to paragraph CD, the wherein score coordinate of ion exchange site III is x=y= 0.35 and z=0.21.

Catalyst of the paragraph CF. according to any one of paragraph CB to CE, wherein by X-ray diffraction, only about half Barium ions can be located in zeolite.

Catalyst of the paragraph CG. according to any one of paragraph CB to CF, the wherein average particle size of catalyst are 60-80 Micron.

A kind of methods preparing microballoon fluidized catalytic cracking catalyst of paragraph CH., the method include：

Wherein：

Methods of the paragraph CI. according to paragraph CH, wherein being carried out with being blended under acidic pH for barium solution.

Methods of the paragraph CJ. according to paragraph CH or paragraph CI, wherein being carried out with being blended under pH=3 for barium solution.

Methods of the paragraph CK. according to any one of paragraph CH to CJ, wherein being blended in higher than room temperature with barium solution At a temperature of or carry out at a temperature of at least about 50 DEG C or at a temperature of about 80 DEG C.

Methods of the paragraph CL. according to any one of paragraph CH to CK, wherein calcining barium-microsphere mixture carry out to It is about 15 minutes or at least about one hour or at least about two hours few.

Methods of the paragraph CM. according to any one of paragraph CH to CL, wherein calcining barium-microsphere mixture is about It is carried out at a temperature of 500 DEG C to about 700 DEG C.

Methods of the paragraph CN. according to any one of paragraph CH to CM, is further contained in before being mixed with barium solution Microsphere is set to be mixed with ammonium salt solution, wherein microsphere includes the Y- zeolites in na form before being mixed with ammonium salt solution.

Methods of the paragraph CO. according to paragraph CN, wherein being carried out with being blended under acidic pH for ammonium salt solution.

Methods of the paragraph CP. according to paragraph CN or paragraph CO, wherein being carried out with being blended under pH=3 for ammonium salt solution.

Methods of the paragraph CQ. according to any one of paragraph CN to CP, wherein being blended in higher than room temperature with barium solution At a temperature of or carry out at a temperature of at least about 50 DEG C or at a temperature of about 80 DEG C.

Methods of the paragraph CR. according to any one of paragraph CH to CQ, further include make the first calcined materials with it is another One ammonium salt solution is mixed to form ammonification material.

Methods of the paragraph CS. according to paragraph CR, wherein with another ammonium salt solution be blended under acidic pH into Row.

Methods of the paragraph CT. according to paragraph CR or paragraph CS, wherein with another ammonium salt solution be blended under pH=3 into Row.

Methods of the paragraph CU. according to any one of paragraph CR to CT, wherein being higher than with being blended in for another ammonium salt solution It is carried out at a temperature of room temperature or at a temperature of at least about 50 DEG C or at a temperature of about 80 DEG C.

Methods of the paragraph CV. according to any one of paragraph CR to CU further includes calcining ammonification material to be formed Second calcined materials.

Methods of the paragraph CW. according to paragraph CV, wherein calcining ammonification material carries out at least about 15 minutes or at least about One hour or at least about two hours.

Methods of the paragraph CX. according to any one of paragraph CV or paragraph CW, wherein calcining ammonification material is at about 500 DEG C To carrying out at a temperature of about 700 DEG C.

Methods of the paragraph CY. according to any one of paragraph CH to CX, further includes steam treatment.

Methods of the paragraph CZ. according to paragraph CY, wherein steam treatment at least about 600 DEG C or at least about 700 DEG C, Or it is carried out at a temperature of at least about 800 DEG C.

Methods of the paragraph DA. according to paragraph CY or paragraph CZ, wherein steam treatment carry out at least about two hours or extremely It is about three hours or at least about four hours few.

Methods of the paragraph DB. according to any one of paragraph CY to DA, wherein steam treatment are in a fluidized bed reactor It carries out.

Paragraph DC. is a kind of as passed through the microballoon fluidized catalytic cracking catalyst prepared by any one of paragraph CH to DB.

Although having been described above and describing some embodiments, it should be appreciated that can be according to the general technology of fields Personnel do not depart from as defined in following claims its it is more broadly in terms of technology in the case of change wherein Become and changes.

It can suitably put into practice in the presence of no any element, limitation or limitation and illustrate herein Property description embodiment, this is not disclosed specifically herein.So that it takes up a position, for example, should widely read and not restrictive Term " including (comprising) ", " including (including) ", " containing (containing) " etc..In addition, used herein Terms and expressions already function as descriptive term term and not restrictive, and are not intended to arrange when using this kind of terms and expressions Except shown and described any equivalent features or part thereof, but will be appreciated that can carry out respectively in required technical scope Kind modification.In addition, phrase " substantially ... forming " is it will be appreciated that include that those specific elements enumerated are not notable with those Influence the other element of the basic and novel features of required technology.Phrase " by ... form " do not include any not specified Element.

For specific embodiment described herein, the disclosure is unrestricted.Such as those skilled in the art It will be evident that many modifications and variations can be carried out in the case of without departing from the spirit and scope.Except listed herein Those of except, those skilled in the art should understand there be within the scope of the present invention functionally equivalent according to being described above Method and composition.This kind of modifications and variations are intended to be within the scope of the appended claims..The disclosure is only by appended power The full breadth of the equivalent that sharp claim and this claims are authorized limits.It should be understood that the present disclosure is not limited to specific Method, reagent, compound composition or biosystem, these are it is of course possible to changing.It should also be understood that term used herein is only Merely to describing specific embodiment and being not intended to be restrictive.

In addition, according to Ma Kushi group (Markushgroups) description characteristic or aspect of the invention, institute The technical staff in category field will be recognized that the disclosure also thus according to any individual member of Ma Kushi group or member's subgroup It is described.

As will be understood by those skilled in the art, for any and all purposes, especially it is provided with written explanation It says, all ranges disclosed herein are also contemplated by its any and all possible subrange and subrange combination.It is any to enumerate Range can be readily recognized because illustrating enough and the same range can be decomposed into it is two parts at least identical, three Part, four parts, five parts, ten parts etc..As non-limiting examples, each range discussed herein can be easily decomposed to lower part three / mono-, intermediate one third and top one third etc..Skilled artisan will also appreciate that all words, such as " at most ", " at least ", " being more than ", " being less than " words similar with its all include cited number and refer to can then as above Discuss and be decomposed into the range of subrange.Finally, those skilled in the art will appreciate that, range include it is each individually at Member.

All disclosures, patent application, publication patent and other documents referenced in this specification are all by reference Be incorporated herein, as each individual disclosures, patent application, publication patent or other documents through it is specific and individually indicate and with The mode being cited in full text is incorporated to generally.With regard to the definition in the disclosure it is inconsistent for, do not include the text that is incorporated by reference It is defined contained in this.

Other embodiments are set forth in following following claims.

Claims

1. a kind of microballoon fluidized catalytic cracking catalyst, including Y- zeolites and barium ions.

2. catalyst according to claim 1, wherein the average particle size of the catalyst be about 60 to about 100 microns or About 60 to about 80 microns or about 70 to about 90 microns.

3. the catalyst according to claim 1 or claim 2, wherein the catalyst has comprising at least about The phase composition of 10wt.%Y- zeolites or at least about 15wt.%Y- zeolites or at least about 18wt.%Y- zeolites.

4. catalyst according to claim 3, wherein the phase composition further includes the amorphous materials of at least about 30wt.% Material or at least about 40wt.% amorphous materials or at least about 50wt.% amorphous materials.

5. catalyst according to claim 4, wherein the amorphous material includes silica-alumina.

6. catalyst according to claim 3, wherein the phase composition further include at least about 20wt.% mullites or At least about 30wt.% mullites.

7. catalyst according to claim 1, wherein the cell parameter of the Y- zeolites is aboutTo aboutOr aboutTo about

8. catalyst according to claim 1, wherein the Y- zeolite unit cells at ion exchange site III comprising barium from Son.

9. catalyst according to claim 1, wherein the Y- zeolite unit cells include at the ion exchange site III 4 barium atoms.

10. catalyst according to claim 1, wherein by x-ray diffraction, the no more than about barium ions energy of half Enough it is located on the Y- zeolites.

11. catalyst according to claim 1, wherein the ion that the barium ions does not occupy the Y- zeolite unit cells is handed over Change place I' and II'.

12. catalyst according to claim 1, wherein the catalyst is comprising at least about 2wt.% barium ions or at least About 3wt.% barium ions.

13. catalyst according to claim 1, wherein the Y- zeolites crystallize on the surface of porous alumina-containing matrix For layer.

14. catalyst according to claim 13, wherein the matrix derives from the kaolin calcined by heat release.

15. a kind of microspherical catalyst including about 3.3wt.% barium ions, wherein the catalyst, which has, includes about 18wt.%Y- The phase composition of zeolite, about 30wt.% mullites, about 2wt.% anatases and about 50wt.% amorphous materials.

16. catalyst according to claim 15, wherein the cell parameter of the Y- zeolites is about

17. according to the catalyst described in claim 15 or claim 16, wherein the catalyst contains in Y zeolites crystalline substance Born of the same parents' intermediate ion exchanges about 4 barium atoms at the III of position.

18. catalyst according to claim 17, wherein the fractional coordinates of the ion exchange site III is x=y= 0.35 and z=0.21.

19. catalyst according to claim 15, wherein by X-ray diffraction, the only about half of barium ions can On the zeolite.

20. catalyst according to claim 15, wherein the average particle size of the catalyst is 60-80 microns.

21. a kind of method preparing microballoon fluidized catalytic cracking catalyst, the method include：

Wherein：

With the barium solution it is described mix before, the microsphere be included in porous alumina-containing matrix surface on crystallize For the Y- zeolites of layer.

22. according to the method for claim 21, wherein be blended under acidic pH described in the barium solution into Row.

23. according to the method described in claim 21 or claim 22, wherein being blended in pH=3 with described in the barium solution Lower progress.

24. according to the method for claim 21, wherein be blended in described in the barium solution higher than room temperature temperature or It is carried out at a temperature of at least about 50 DEG C or at a temperature of about 80 DEG C.

25. according to the method for claim 21, wherein calcine the barium-microsphere mixture carry out at least about 15 minutes, Or at least about one hour or at least about two hours.

26. according to the method for claim 21, wherein calcining the barium-microsphere mixture is up to about 700 DEG C at about 500 DEG C At a temperature of carry out.

27. according to the method for claim 21, be further contained in the barium solution it is described mix before, make described Microsphere is mixed with ammonium salt solution, wherein including the Y- in na form with the foregoing description microsphere that mixes of the ammonium salt solution Zeolite.

28. according to the method for claim 27, wherein be blended in described in the ammonium salt solution under acidic pH into Row.

29. according to the method described in claim 27 or claim 28, wherein being blended in pH=3 with described in the ammonium salt solution Lower progress.

30. according to the method for claim 27, wherein be blended in described in the ammonium salt solution higher than room temperature temperature or It is carried out at a temperature of at least about 50 DEG C or at a temperature of about 80 DEG C.

31. according to the method for claim 21, further including makes first calcined materials be mixed with another ammonium salt solution To form ammonification material.

32. according to the method for claim 31, wherein be blended in described in another ammonium salt solution under acidic pH into Row.

33. according to the method for claim 31, wherein being carried out with being blended in described in another ammonium salt solution under pH=3.

34. according to the method for claim 31, wherein with another ammonium salt solution it is described mix at temperatures greater than room temperature, Or it is carried out at a temperature of at least about 50 DEG C or at a temperature of about 80 DEG C.

35. according to the method for claim 31, further including the calcining ammonification material to form the second calcined materials.

36. according to the method for claim 35, being carried out at least about 15 minutes or at least about wherein calcining the ammonification material One hour or at least about two hours.

37. according to the method for claim 35, wherein calcining temperature of the ammonification material at about 500 DEG C to about 700 DEG C Lower progress.

38. according to the method for claim 21, further including steam treatment.

39. according to the method for claim 38, wherein the steam treatment at least about 600 DEG C or at least about 700 DEG C, Or it is carried out at a temperature of at least about 800 DEG C.

40. according to the method described in claim 38 or claim 39, wherein the steam treatment carry out at least about two hours, Or at least about three hours or at least about four hours.

41. the method according to any one of claim 38 to 40, wherein the steam treatment is in a fluidized bed reactor It carries out.

42. microballoon fluidized catalytic cracking catalyst prepared by a kind of method by described in any one of claim 21 to 41.